U.S. patent application number 12/390015 was filed with the patent office on 2009-09-17 for apparatus and method for extracting petroleum from underground sites using reformed gases.
This patent application is currently assigned to PIONEER ENERGY, INC.. Invention is credited to Mark H. Berggren, Robert M. Zubrin.
Application Number | 20090229815 12/390015 |
Document ID | / |
Family ID | 38557147 |
Filed Date | 2009-09-17 |
United States Patent
Application |
20090229815 |
Kind Code |
A1 |
Zubrin; Robert M. ; et
al. |
September 17, 2009 |
Apparatus and Method for Extracting Petroleum from Underground
Sites Using Reformed Gases
Abstract
Methods and apparatus for removing oil or natural gas from the
ground. In one example, the method may include reforming a fuel
source by reaction with water to generate driver gas, and injecting
the driver gas into the oil well. The reforming operation may
include causing the combustion of a combustible material with
ambient oxygen for the release of energy; and heating a reforming
reaction fuel and water sources, with the energy released from the
combustion of the combustible material, to a temperature above that
required for the reforming reaction wherein the fuel and water
sources are reformed into driver gas. In one example, the amount of
the combustible material combusted is sufficient to result in the
release of enough energy to heat an amount of the reforming
reaction fuel and water sources to the temperature above that
required for the reforming reaction to proceed. The driver gas may
be used to help extract oil from the ground and especially oil from
depleted oil wells. It may also be used to drive natural gas
trapped underground or in coal beds to the surface.
Inventors: |
Zubrin; Robert M.;
(Lakewood, CO) ; Berggren; Mark H.; (Lakewood,
CO) |
Correspondence
Address: |
SWANSON & BRATSCHUN, L.L.C.
8210 SOUTHPARK TERRACE
LITTLETON
CO
80120
US
|
Assignee: |
PIONEER ENERGY, INC.
Lakewood
CO
|
Family ID: |
38557147 |
Appl. No.: |
12/390015 |
Filed: |
February 20, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11392898 |
Mar 29, 2006 |
7506685 |
|
|
12390015 |
|
|
|
|
Current U.S.
Class: |
166/105.5 |
Current CPC
Class: |
E21B 43/168 20130101;
B01J 19/14 20130101; E21B 43/164 20130101; Y02P 90/70 20151101 |
Class at
Publication: |
166/105.5 |
International
Class: |
E21B 43/00 20060101
E21B043/00 |
Claims
1. An apparatus for removing oil from an oil well, comprising: a
first storage container for storing a combustible material; a
second storage container for storing a reforming reaction fuel
source; a third container for storing water for reaction with the
reforming fuel. a first chamber having an inlet and an outlet, the
first chamber for combusting the combustible material with ambient
oxygen for the release of energy, the inlet of the first chamber
fluidly coupled with the first storage container; and a second
chamber having an inlet and an outlet, the inlet of the second
chamber fluidly coupled with the second and third storage
containers, a portion of the second chamber positioned within a
portion of the first chamber, the second chamber fluidly isolated
from the first chamber; wherein the energy released in the first
chamber heats the reforming reaction fuel and water sources in the
second chamber to a temperature above the reforming reaction fuel
source's vaporization point thereby reforming fuel source into
driver gas exiting the outlet of the second chamber.
2. The apparatus of claim 1, wherein the second storage container
includes a mixture of water with the reforming reaction fuel
source.
3. The apparatus of claim 1, wherein the first chamber includes an
igniter for igniting the combustible material.
4. The apparatus of claim 1, wherein the second chamber is adapted
to receive a catalyst to reduce the amount of energy required to
heat the reforming reaction fuel and water source to a temperature
above which the reforming reaction will proceed.
5. The apparatus of claim 1, wherein the driver gas includes
hydrogen gas.
6. The apparatus of claim 1, wherein the combustible material and
reforming reaction fuel source are the same.
7. The apparatus of claim 1, wherein the combustible material
and/or reforming reaction fuel source are an alcohol.
8. The apparatus of claim 1, wherein the combustible material
and/or reforming reaction fuel source are a crude petroleum
product.
9. The apparatus of claim 1, wherein the combustible material
and/or reforming reaction fuel source are a refined petroleum
product.
10. The apparatus of claim 1, further comprising: a first heat
exchanger coupled with the outlet of the first chamber and
thermodynamically coupled with the inlet or interior of the second
chamber, the first heat exchanger for heating the reforming
reaction fuel source.
11. The apparatus of claim 1, further comprising: a second heat
exchanger coupled with the outlet of the second chamber and
thermodynamically coupled with the inlet of the second chamber, the
second heat exchanger for pre-heating the reforming reaction fuel
source and for cooling the driver gas.
12. The apparatus of claim 1 wherein a heat exchanger is positioned
within the second chamber, and gases entering this heat exchanger
from the first chamber are used to heat the second chamber to the
temperature required for the reforming reaction to proceed.
13. An apparatus for producing driver gas used in the removal of
oil from an oil well, comprising a reaction chamber for combining a
reformer fuel, an oxidizing agent and water, the reaction chamber
having at least one inlet for receiving the reformer fuel,
oxidizing agent and water and at least one outlet for release of
the produced driver gas.
14. The apparatus of claim 13, further comprising: a heating
element for heating the reaction chamber to a predetermined
temperature required to perform an autothermal reforming reaction
between the reformer fuel, oxidizing agent and water.
15. The apparatus of claim 13, further comprising: a counter-flow
heat exchanger to transfer heat from the released driver gas to the
incoming reformer fuel.
16. The apparatus of claim 13, further comprising: a catalyst bed
integrated within the reaction chamber to facilitate the
autothermal reformer reaction between the reformer fuel, oxidizing
agent and water.
17. The apparatus of claim 1, wherein the reforming reaction fuel
source and/or combustible material include coal and/or a derivative
of coal.
18. The apparatus of claim 13, wherein the reforming reaction fuel
source and/or combustible material include coal and/or a derivative
of coal.
19. The apparatus of claim 1, wherein the reforming reaction fuel
source and/or combustible material include wood.
20. The apparatus of claim 13, wherein the reforming reaction fuel
source and/or combustible material include wood.
Description
RELATED APPLICATIONS
[0001] This application claims priority to U.S. patent application
Ser. No. 11/392,898 entitled "Apparatus and Method for Extracting
Petroleum from Underground Sites Using Reformed Gases" filed Mar.
29, 2006, the disclosure of which is hereby incorporated by
reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to extraction of underground gasses
and liquids and more particularly to petroleum and/or natural gas
extraction using reformed gas.
BACKGROUND OF THE INVENTION
[0003] Currently there are thousands of depleted oil and natural
gas wells in the United States, which collectively possess
significant amounts of petroleum resources that cannot currently be
extracted using conventional extraction techniques.
[0004] Accordingly, as recognized by the present inventors, what is
needed is a method and apparatus for extracting oil/petroleum from
the ground or from oil wells, such as depleted oil wells.
[0005] It is against this background that various embodiments of
the present invention were developed.
BRIEF SUMMARY OF THE INVENTION
[0006] In light of the above and according to one broad aspect of
one embodiment of the present invention, disclosed herein is a
method for generating and using hydrogen and carbon dioxide rich
gas mixtures for driving oil from an oil well. In addition, and in
accordance with another broad aspect of an embodiment of the
present invention, disclosed herein is a method for generating and
using hydrogen and carbon dioxide gas mixtures for driving trapped
natural gas out of the ground.
[0007] In one example, the methods of the invention include
reforming or reacting a fuel or other hydrocarbon source with water
to generate hydrogen-carbon dioxide rich "driver gas" mixtures and
injecting the driver gas into the oil well. The fuel or hydrocarbon
sources used for generation of driver gas include, but are not
limited to, alcohols, olefins, paraffins, ethers, aromatic
hydrocarbons, and the like. In addition, the fuel sources can be
from refined commercial products such as propane, diesel fuels,
gasolines or unrefined commercial products such as crude oil or
natural gas. The water can be introduced into the reforming reactor
as liquid water, as steam, or, if the fuel is an alcohol or other
substance miscible in water, as a component premixed with the
fuel.
[0008] In preferred embodiments the fuel source for the reforming
reaction is an unrefined product such as crude oil, and in some
embodiments, a crude oil captured from the same oil well where the
driver gas is being injected.
[0009] The reforming reaction can be driven by the release of
energy from a combustible or non-combustible source such as
electricity. In preferred embodiments the energy is provided by a
combustion reaction using a combustible material, and atmospheric
air.
[0010] In preferred embodiments the driver gas is a hydrogen-carbon
dioxide rich gas mixture.
[0011] The method may also include the addition of a catalyst to
the reforming reaction. The catalyst reduces the temperature
required to reform the fuel source.
[0012] According to another broad aspect of another embodiment of
the present invention, disclosed herein is an apparatus for
removing oil from an oil well. In one example, the apparatus may
include a first storage container for storing a combustible
material used in the combustion reaction; a second storage
container for storing a fuel or alternative hydrocarbon source used
in the reforming reaction; a third storage container for water to
be reacted with fuel in the reformer; a first chamber having an
inlet and an outlet, the first chamber for combusting the
combustible material with ambient oxygen for the release of energy,
the inlet of the first chamber fluidly coupled with the first
storage container; and a second chamber having an inlet and an
outlet, the inlet of the second chamber fluidly coupled with the
second and third storage containers, a portion of the second
chamber positioned within a portion of the first chamber, the
second chamber fluidly isolated from the first chamber. In one
example, the energy released in the first chamber heats the fuel
and water sources used in the reforming reaction in the second
chamber to a temperature above that necessary for the reforming
reaction thereby reforming the fuel and water sources into driver
gas exiting the outlet of the second chamber.
[0013] In one example, the first chamber includes an igniter for
igniting the combustible material, and the second storage container
may include a mixture of water with the reforming reaction fuel
source. The second chamber may be adapted to receive a catalyst to
reduce the temperature and amount of energy required to heat the
reforming reaction fuel and water sources to a temperature above
that necessary for the reforming reaction to proceed.
[0014] In another embodiment, the apparatus may include a first
heat exchanger coupled with the outlet of the first chamber and
thermodynamically coupled with the second chamber, the first heat
exchanger for pre-heating the reforming reaction fuel and/or water
sources. The apparatus may also include a second heat exchanger
coupled with the outlet of the second chamber and thermodynamically
coupled with the inlet of the second chamber, the second heat
exchanger for pre-heating the reforming reaction fuel and or water
sources and for cooling the generated driver gas.
[0015] According to another broad aspect of another embodiment of
the present invention, disclosed herein is an autothermal apparatus
for generating driver gas to remove oil from an oil well. In one
example, the apparatus may include a single reaction chamber for
combining a reforming fuel source, water, and an oxidizer; a
reforming reaction fuel delivery pipe for delivery of the reforming
fuel source; another pipeline for water; an oxidizing agent
delivery pipe for delivery of oxygen or other like oxidizing agent;
and a driver gas outlet port for removal of driver gas produced in
the reaction chamber. In one example, a counter-flow heat exchanger
provides energy/heat from the released driver gas to the incoming
reformer fuel to facilitate the autothermal reformer reaction in
the reaction chamber.
[0016] In one example of the autothermal reformer apparatus, a
reaction chamber heater pre-heats the reaction chamber to initiate
the reforming reaction and subsequent formation of driver gas. In
another example, the reaction chamber includes a catalyst bed to
facilitate autothermal reforming of appropriate reforming fuel
sources.
[0017] The features, utilities and advantages of the various
embodiments of the invention will be apparent from the following
more particular description of embodiments of the invention as
illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 illustrates an example of an embodiment of the
present invention for the extraction of oil from an oil well, in
accordance with one embodiment of the present invention.
[0019] FIG. 2 illustrates an example of operations for extracting
oil from an oil well, in accordance with one embodiment of the
present invention.
[0020] FIG. 3 illustrates an example of an apparatus for extracting
oil from an oil well, in accordance with one embodiment of the
present invention.
[0021] FIG. 4 illustrates another example of an apparatus for
extracting oil from an oil well, in accordance with one embodiment
of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0022] Embodiments of the present invention provide for the
creation of driver gas which is used for extracting oil from an
otherwise depleted oil well, or to drive trapped reservoirs of
underground natural gas to the surface. For purposes of the present
invention a driver gas is typically any gas formed during the
reforming reactions of the present invention and is preferably a
hydrogen-rich gas or hydrogen and carbon dioxide containing gas.
Various embodiments of the present invention are disclosed herein.
Note that the majority of the disclosure is directed toward
creating a driver gas that is ultimately injected into depleted oil
wells for the extraction of oil, however, methods and apparatus of
the invention can also be used to create driver gases useful in
driving trapped natural gas to the surface. As such, it is noted
that the scope of the present invention encompasses the use of
driver gas created in accordance with the present invention to
drive out other materials beyond oil from depleted oil wells, and
in particular encompasses using driver gas to drive trapped natural
gas out of underground natural gas reservoirs.
[0023] In FIG. 1, a below-ground oil well 100 (which may be
otherwise depleted) is illustrated, having an amount of oil therein
such as a residual amount of oil. A portable, self-contained
reformer 102 in accordance with the present invention generates
driver gas (shown as arrow 104) which may be pumped into the oil
well for removing the residual oil from the oil well. As explained
herein, the reformer 102 may reform or react fuel sources (shown as
arrow 105) such as alcohols, olefins, paraffins, ethers, aromatic
hydrocarbons, and other like materials (or mixtures thereof) with
(shown as arrow 107) (or without) water to form driver gas which,
in one example, is hydrogen and carbon dioxide rich gas mixture.
The driver gas is then compressed by a compressor 106 into high
pressure gas that could be pumped underground (see line 108) where
it could impose pressure on residual underground petroleum 109
sufficient to allow it to be extracted by a nearby oil well 110 or
other like site.
[0024] FIG. 2 illustrates an example of operations which may be
performed in order to drive petroleum resources out of the ground,
such as out of an oil well or a depleted oil well. At operation 1
(shown as box 200), a fuel source is reformed into driver gas. In
one example, operation 1 may include combustion of a material 202
such as methanol or ethanol, in order to provide energy, for
instance, within a combustion chamber. The energy generated from
the combustion may be used to heat the reforming reaction fuel
source to a temperature where the fuel source reacts with (or
without) water to form a hydrogen-rich driver gas 204. Note that
the energy required to drive the reforming reaction can also be
provided from a non-combustible source, for example, solar energy,
nuclear energy, wind energy, grid electricity, or hydroelectric
power 206.
[0025] At operation 2 (shown as box 208), the driver gas is
injected into the oil well in order to drive petroleum out of the
ground 210. For instance, the injected gas could soften highly
viscous petroleum residues and displace them, thereby mobilizing
such petroleum residues for recovery by conventional means 212.
[0026] Embodiments of the present invention provide reformer
apparatus for generating driver gas used in petroleum extraction,
from among other sites, depleted oil wells. Apparatus embodiments
of the invention are portable, self-contained and energy efficient,
able to generate driver gas through reforming of a fuel source.
Each apparatus utilizes a reforming reaction to generate the driver
gas and a combustion reaction to provide the energy required to
reform a fuel and generate the driver gas. Various apparatus
embodiments are provided herein based on either separating the
reforming reaction from the combustion reaction or based on
combining the reforming reaction with the combustion reaction
(referred to herein as autothermal reforming). In addition, the
apparatus typically includes heat exchange elements to facilitate
heat transfer from the high temperature driver gas to incoming
reformer and/or combustion fuel. The transfer of heat facilitating
the reforming reaction and lowering the energy required to complete
the driver gas formation. Note that various apparatus
configurations are envisioned to be within the scope of the present
invention as long as the apparatus provides for on-site, portable,
energy efficient reforming reactions (and preferably steam
reforming reactions) that produce driver gas useful in the
extraction of petroleum products from an underground source. As
such, a first illustrative embodiment is described in FIG. 3 for
separate reformer and combustion reactions, followed by an
embodiment described in FIG. 4 for autothermal reforming and
production of driver gas from a single reaction chamber.
Reformer Apparatus
[0027] FIG. 3 illustrates an example of a self-contained, portable
apparatus 300 for generating driver gas (shown as arrow 302) for
injection into the ground or an oil well, in accordance with one
embodiment of the present invention.
[0028] In FIG. 3, an embodiment of the apparatus may include a
first storage container 304 storing a combustible material, such as
an alcohol or olefin. A second storage container 306 is also
provided, which may include a reforming reaction fuel source, such
as an alcohol, olefin, paraffin, and the like or mixtures thereof.
If the reformer fuel is an alcohol or other chemical miscible in
water, the water may be mixed with the fuel in this container. If
the reformer fuel is a hydrocarbon such as a paraffin not miscible
in water, a third container (not shown) is required for the water
to be reacted with the fuel in the reformer chamber.
[0029] In one example, a first chamber 304 has an inlet port 308
and an outlet port 310 and is adapted to provide for the combustion
of the combustible material. In one example, the first chamber
includes an igniter such as a spark plug 312 or other conventional
igniter, and a nozzle 314 coupled with the inlet port 308 of the
first chamber 304. The inlet port 308 of the first chamber may be
coupled with the first storage container so that the contents of
the first storage container may be introduced into and combusted
within the first chamber. The first chamber also includes a port
316 for introducing combustion air into the first chamber. The
first chamber is also adapted to receive a portion of the second
chamber 306, described below, so that the energy/heat from the
combustion of the combustible material from the first storage
container within the first chamber is transferred into a portion of
the second chamber. The outlet port 310 of the first chamber, in
one example, is near the inlet port of the second chamber (not
shown), and a heat exchanger is used to allow the combustion
exhaust gas to heat the fuel and water entering the second chamber.
Alternatively, the outlet of the first chamber can feed to a heat
exchanger 318 located inside the second chamber, which thereby
allows the combustion exhaust gases produced in the first chamber
to provide the heat to drive the reforming reactions in the second
chamber.
[0030] The second chamber 306 has an inlet port (shown as arrow
320) and an outlet port 302. In one example, the inlet port is
coupled with the second storage container and receives the contents
of the second and third storage containers. The second chamber may
also include a port 322 for receiving catalyst material within the
second chamber.
[0031] In one example, the second chamber is positioned within the
first chamber, such that the combustion heat/energy from the first
chamber heats the reforming reaction fuel and water sources
contained within the second chamber to a point where the fuel
source vaporizes and reforms into a driver gas which exists out of
the outlet port of the second chamber. In one example, the first
and second chambers are fluidly isolated.
[0032] A catalyst 324 may be utilized within the second chamber in
order to reduce the temperature and amount of energy required to
heat the reforming reaction fuel and water sources to their
reaction temperature, and such catalysts are dependent upon the
fuel source but include iron based catalyst, zinc oxide, copper
based catalyst, alumina, and the like.
[0033] In one example, a first heat exchanger 318 is coupled with
the outlet port of the first chamber (the combustion chamber) and
is thermodynamically coupled with a portion of the inlet port of
the second chamber. In this manner, the hot combustion exhaust
gases from the first chamber are used to preheat the reforming
reaction fuel and or water sources as they are being introduced
into the second chamber for vaporization/reformation into a driver
gas.
[0034] A second heat exchanger 326 may also be utilized, wherein
the second heat exchanger 326 is thermodynamically coupled with the
outlet ports 302 and the inlet port 320 of the second chamber,
which provides the dual benefit of preheating the reforming
reaction fuel and/or water sources prior to entry into the second
chamber, as well as cooling the driver gas which is expelled from
the outlet ports of the second chamber. Note that various
illustrative temperatures are shown to illustrate heat-exchange,
but are not meant to limit the range of temperatures useful in the
present invention.
[0035] FIG. 4 illustrates another example of a self-contained
portable apparatus 400 for generating driver gas for injection into
the ground or an oil well, in accordance with another embodiment of
the present invention. The embodiment illustrated in FIG. 4
provides what the inventors term an "autothermal reformer" for the
production of driver gas which is injected into the ground or an
oil well (to remove oil or natural gas or other like
materials).
[0036] An autothermal reformer 400 of the present invention
directly reacts a reformer fuel source with oxygen or other like
oxidizers in a single chamber 402. Embodiments of the reformer
provide an environment for reforming a fuel source with a feed at
proper temperature and pressure resulting in the release of driver
gas. Since the reforming reaction is favored by low pressure, in
preferred embodiments pressure in the autothermal reactor should be
kept under 50 bar. Embodiments of the autothermal reformer combine
counter-flow heat exchange elements to enhance heat transfer and
energy efficiency of the autothermal reformer.
[0037] FIG. 4 shows one embodiment of the autothermal reformer
apparatus 400 of the invention. Note that other autothermal
reformer apparatus are envisioned to be within the scope of the
present invention as long as they provide at least a reaction
chamber with a reforming reaction fuel source inlet, an air or
oxidizing agent inlet and a driver gas outlet.
[0038] Referring to FIG. 4, an autothermal reformer apparatus 400
is shown having a reaction chamber 402, a reforming reaction fuel
delivery pipe (fuel pipe) 404 for delivery of a reforming reaction
fuel, a driver gas outlet port (outlet port) 406 for release of
produced driver gas, and an oxygen or other like gas inlet pipe
(gas pipe) 408 for delivery of a gas used in the combustion of the
reforming reaction fuel in the reaction chamber.
[0039] Still referring to FIG. 4, the reaction chamber 402 is of
sufficient size and shape for autothermal reforming of a fuel
source. Different chamber geometries can be used as long as they
constrain the autothermal reforming reactions of the present
invention and provide sufficient chamber space to produce an amount
of driver gas necessary at an oil extraction site. A catalyst bed
(see below) 410 is typically integrated into the reaction chamber
for optimized autothermal reforming reactions. In the embodiment
shown in FIG. 4, The fuel pipe 404 is coupled to the outlet port to
form a counter-exchange heat exchanger 412 so that the energy/heat
from the exiting driver gas is transferred to the reforming fuel
entering the reaction chamber via the fuel pipe. In addition, the
fuel pipe 404 typically enters at a first or top end 414 of the
reaction chamber and releases the fuel toward the second or bottom
end 416 of the reaction chamber. This configuration enhances heat
release from the heated reformer fuel into the contents of the
reaction chamber. Release of fuel into the chamber 402 can be via a
nozzle 415 or other like device. The gas pipe 408 is typically
coupled to or adjacent to the fuel pipe and releases the oxygen or
other like gas adjacent to the release of the reformer fuel 417.
Note that other configurations of reformer fuel and water delivery,
oxygen or other oxidizing agent delivery and driver gas release are
envisioned to be within the scope of the invention and are shown in
FIG. 4 as an illustration of one embodiment.
[0040] In use, the reaction chamber of the autothermal reformer
apparatus is typically preheated to a temperature sufficient to
start the reforming reaction, i.e., between 200.degree.
C.-400.degree. C. Preheating can be accomplished by a reaction
chamber integrated heating element, a heating coil, an external
combustor heating system, or other like device (not shown).
[0041] The reformer fuel source (with or without water, see below)
is fed into the reaction chamber via the fuel pipe 404. Note that
once driver gas is produced in the reaction chamber, the reformer
fuel is heated prior to delivery into the reaction chamber by the
exiting driver gas (shown as arrow 418) via the counter-flow heat
exchanger. At approximately the same time that the reformer fuel is
being delivered to the reaction chamber, the oxygen or other
oxidizing agent being delivered to the reaction chamber via the
inlet pipe. Various reformer chemical reactions are described
below.
[0042] Once the reforming reaction has been established within the
reaction chamber the reaction chamber heating element may be shut
off to conserve energy. Note also that the amount of water combined
into the reforming fuel can be adjusted to control the reforming
temperatures.
Chemical Processes
[0043] The generation of driver gas(es) will now be described, for
example generating hydrogen rich gas, i.e., a mixture of hydrogen
gas (H.sub.2), carbon monoxide (CO) and/or carbon dioxide
(CO.sub.2). The constituents of driver gas produced by embodiments
of the present invention is determined by the reaction constituents
and conditions as described below, but generally include at least
hydrogen gas.
[0044] Embodiments of the present invention provide processes for
producing driver gas from the reforming of select fuel sources,
such as solid, liquid and/or gaseous hydrocarbons, alcohols,
olefins, paraffins, ethers, and other like materials. Illustrative
fuel sources for use in the reforming reaction include, but are not
limited to, methanol, ethanol, propane, propylene, toluene and
octane.
[0045] The combustor fuel can include both refined commercial
products such as propane, diesel fuel, and/or gasoline, or
unrefined substances such as crude oil, natural gas, coal, or wood.
In preferred embodiments the driver gas mixture is generated from
the steam reforming of fuels such as methanol or ethanol. In other
preferred embodiments the driver gas is generated by reforming
unrefined hydrocarbon sources such as crude oil, especially crude
oil obtained from the oil well site where the driver gas is being
injected.
[0046] The methods of the invention are reproducible and easily
performed in the portable inventive devices described herein. The
processes of the invention are superior to electrolytic hydrogen
generation which require large amounts of electrical power and are
typically non-portable. The preferred processes of the invention
are also superior to the production of hydrogen by cracking or
pyrolyzation of hydrocarbons without the use of water because much
more driver gas is produced for a given amount of fuel
consumed.
[0047] The methods of the invention use easily obtained fuel
sources such as a hydrocarbon sources, water, and atmospheric
air.
[0048] Embodiments of the invention also include combustible
materials to supply the energy to drive the reforming reactions of
the present invention. Combustible reactions can include a source
of energy that is burned with ambient oxygen for the release of
energy. Note that in alternative embodiments of the invention, the
energy required to drive the reforming reactions of the invention
can be provided by non-combustion sources, such as solar, nuclear,
wind, grid electricity, or hydroelectric power.
[0049] In some embodiments of the invention, the reforming reaction
to generate hydrogen rich gas and combustion reactions to drive
that reaction both incorporate the same fuel. For example, methanol
can be used as the reforming fuel source and as the source of
combustion to drive the reforming reaction.
[0050] In more detail, the invention provides reforming processes
of any reforming fuel source to generate, for example, H.sub.2, CO
and/or CO.sub.2. The driver gas forming reactions of the invention
are endothermic, requiring an input of energy to drive the reaction
toward fuel reformation.
[0051] In one embodiment, the energy required to drive the
reforming reaction is provided through the combustion of any
combustible material, for example an alcohol, a refined petroleum
product, crude petroleum, natural gas, wood, or coal that provides
the necessary heat to drive the endothermic steam reforming
reaction.
[0052] In another embodiment, the energy required to drive the
reforming reaction is provided via any non-combustible source
sufficient to generate enough heat to drive the reforming reaction
to substantial completion.
[0053] The present combination of reforming and combustion
reactions can be performed within a portable reaction vessel, for
example the devices described herein (see FIG. 3 and FIG. 4). This
is in contrast to electrolysis hydrogen gas formation which
requires large amounts of electrical power and non-portable
machinery for the generation of the gas.
[0054] The following reactions provide illustrative processes for
reforming a fuel source to produce a driver gas used in the
recovery of oil or other like materials. Several illustrative
combustion reactions that provide the energy required to drive
those reforming reactions are also provided. In one embodiment,
provided as Reaction 1, a hydrogen rich gas is formed using pure
methanol. Note that the reforming reaction and combustion reaction
can be performed in separate reaction chambers (see FIG. 3) or can
be combined and performed in a single reaction chamber (see FIG.
4). The following 12 reactions illustrate a separation of the
reforming and combustion reactions, however, as is shown in FIG. 4
and discussed in greater detail below, an autothermal reforming
reaction can be accomplished by directly reacting the fuel sources
of the invention with oxygen in a single reaction chamber. These
autothermal reactions can be performed in the presence or absence
of water.
[0055] Separate chamber reactions (see FIG. 3):
CH.sub.3OH.fwdarw.CO+2H.sub.2 Reaction 1
[0056] Reaction 1 comes with an .DELTA.H of +128.6 kJoules/mole.
This means that this same amount of energy must be contributed by
the combustion reaction to drive the reaction toward the formation
of CO and H.sub.2.
[0057] In an alternative embodiment, the reformed fuel, e.g.,
methanol, can be mixed with water as shown in reaction 2:
CH.sub.3OH+H.sub.2O.sub.(e).fwdarw.CO.sub.2+3H.sub.2 Reaction 2
[0058] Reaction 2 comes with an .DELTA.H of +131.4 kJoules/mole. As
above in Reaction 1, for a small price in energy, an appropriate
fuel source can be cracked to form hydrogen gas, carbon monoxide
and/or carbon dioxide. If we compare Reaction 2 to Reaction 1, we
observe that for essentially the same energy, the use of water
allows the hydrogen yield to be increased by 50%. This is why it is
generally advantageous to employ both water and fuel in the
proposed reforming system.
[0059] Reactions 3-8 illustrate several other reforming reaction
fuel reactions that are in accordance with the present
invention.
C.sub.2H.sub.5OH+3H.sub.2O.fwdarw.2CO.sub.2+6H.sub.2 Reaction 3
(ethanol)
C.sub.3H.sub.8+6H.sub.2O.fwdarw.3CO.sub.2+10H.sub.2 Reaction 4
(propane)
C.sub.3H.sub.6+6H.sub.2O.fwdarw.3CO.sub.2+9H.sub.2 Reaction 5
(propylene)
C.sub.7H.sub.8+14H.sub.2O.fwdarw.7CO.sub.2+18H.sub.2 Reaction 6
(toluene)
C.sub.8H.sub.18+16H.sub.2O .fwdarw.8CO.sub.2+25H.sub.2 Reaction 7
(octane)
CH.sub.4+2H.sub.2O.fwdarw.CO.sub.2+4H.sub.2 Reaction 8
(methane)
[0060] Note that in general Reactions 1-8 (as well as other
reforming reactions of the invention) result in large increases in
the number of molecules of products compared to reactants, so all
are benefited by being performed under low pressure.
[0061] In alternative embodiments the reforming reaction is
performed in the presence of a catalyst, for example, when the
reforming reaction fuel is an alcohol, e.g., methanol or ethanol,
which is combined with water, the feed is passed over a copper on
alumina, copper on zinc oxide, or other copper-based catalyst at
temperatures above 250.degree. C. (although better results may be
obtained at higher temperatures). Thus, for example, the reactor
chamber in FIG. 4 could be prepared with a copper on zinc oxide
catalyst when the reformer fuel is an alcohol.
[0062] When the reforming reaction fuel is a hydrocarbon, e.g.,
paraffins, olefins, aromatics, combined with water, the feed is
passed over an iron based catalyst at temperatures above
300.degree. C. (although better results may be obtained at higher
temperatures).
[0063] When the reforming reaction fuel is methane combined with
water, the feed is passed over a nickel or ruthenium based catalyst
at temperatures above 500.degree. C. (although better results may
be obtained at higher temperatures).
[0064] In some embodiments, combinations of olefins, paraffins, and
aromatics (as found in crude petroleum) can be used as the
reforming reaction fuel source. In other embodiments, a crude
petroleum product is used as the reforming reaction fuel source
where the crude petroleum product is first treated to remove sulfur
or other impurities (sulfur can poison catalyst involved with the
reforming reaction). Note that other reforming reaction fuel
sources may also need to be pre-treated for removal or sulfur or
other impurities, for example, natural gas.
[0065] In another embodiment of the invention, a reforming reaction
fuel source can be generated from a pre-source. In one example,
gamma alumina is used to react dimethyl ether with water to make
methanol via Reaction 9:
(CH.sub.3).sub.2O+H.sub.2O.fwdarw.2CH.sub.3OH Reaction 9
[0066] The methanol produced in Reaction 9 can then be reacted with
more water via Reaction 2 to produce the driver gas used to obtain
oil from depleted oil wells, for example. As such, using a mixed
gamma alumina and copper catalyst bed, dimethyl ether and water are
reacted to obtain the net result shown in Reaction 10:
(CH.sub.3).sub.2O+3H.sub.2O.fwdarw.2CO.sub.2+6H.sub.2 Reaction
10
[0067] The energy required to drive the reforming reactions is
provided by either combustible or non-combustible sources. In
preferred reactions the energy is provided by combustion of a
combustible material and in some embodiments the combustible
material is the same as the reforming reaction fuel source.
[0068] An illustrative combustion reaction is shown in Reaction 11.
The combustion of a source of fuel supplies the energy to drive
reactions 1-10. An illustrative example is the combustion of
methanol with ambient oxygen to release .DELTA.H of -725.7
kJoules/mole. Reaction 11 is shown below:
CH.sub.3OH.sub.(e)+ 3/2O.sub.2.fwdarw.CO.sub.2+2H.sub.2O.sub.(e)
Reaction 11
[0069] Thus, theoretically (not being bound by any particular
theory) for purposes of this illustration, only 1/5 of the mass of
methanol is required to be burned to reform methanol via reactions
1 and/or 2. This is a small price to pay given that most fuels used
in the reforming reaction are cheap, easy to store as a liquid and
readily available, even in remote areas of the world.
[0070] In general, the required energy to drive the reforming
reactions of the present invention can be furnished by burning
small fractions of the reforming reaction fuel source or by using
an alternative fuel or other heating methods such as nuclear, solar
or electric grid power. In each case, a much larger number of
product molecules is produced than is burned or reacted, allowing a
much larger amount of fuel to be driven out of the ground than must
be used to obtain it. The driver gas consists of mixtures of
hydrogen and carbon dioxide, neither of which will react with
petroleum, and both of which can serve to reduce its viscosity and
provide pressure to drive the petroleum from the ground.
[0071] In yet another embodiment, carbon monoxide derived from
various reforming reactions is separated away from the hydrogen gas
using a "membrane" or other separation device and further burned to
provide additional energy to drive the methanol reforming, see
Reaction 12.
CO+1/2O.sub.2.fwdarw.CO.sub.2 Reaction 12
[0072] The burning of CO results in the .DELTA.H of -283.0
kJoules/mole, again releasing heat for use in driving the reforming
reactions illustrated in Reactions 1-10.
[0073] With regard to autothermal reforming, a reforming fuel is
directly reacted with oxygen in the presence or absence of water.
In alternative embodiments to facilitate combustion of all of the
reforming fuel, oxygen gas, air, or alternative oxidizer materials,
e.g., hydrogen peroxide, nitrous oxide, is metered in an amount to
react with all of the carbon contained in the reforming fuel. The
thermodynamics of the autothermal chemical reactions and the
presence of a proper catalyst with proper selection of operating
temperature and pressure result in formation of substantially only
carbon dioxide and hydrogen gas. However, in use, small amounts of
water and other compounds may form by combustion of hydrogen or
other byproduct reactions. Where air is used as the oxidizer, there
will also be nitrogen left over which can serve as part of the
driver gas.
[0074] As discussed in greater detail throughout the present
disclosure, the reforming of fuel is provided for production of
driver gas used in the extraction of oil from the ground or from an
oil well. In one embodiment, the generated driver gas, e.g.,
hydrogen rich gas, is used for recovering materials from currently
economically non-viable resources, including extracting oil trapped
in depleted wells, liquefying oil shale, and forcing out methane
trapped in coal beds. Currently there are thousands of depleted oil
wells in the United States, which collectively possess billions of
barrels of petroleum resources that cannot conventionally be
extracted by economic means.
[0075] The driver gas of the present invention is injected into the
ground, where it softens highly viscous petroleum residues and
displaces and mobilizes them for economic recovery.
[0076] These uses compare with the use of helium or other stored
compressed gases as driver gas at an oil well recovery site.
However, such gases are normally transported at very high pressures
(2200 psi) and in very heavy gas bottles (e.g. K-bottles, .about.55
kg each with, for example, 1.1 kg of He). Using easily transported
methanol to perform Reaction (1) or (2), or better yet, crude
petroleum from the site itself, allows the production of a
high-hydrogen-concentration gas without a large electrical
requirement needed for electrolytic gas generators. In this sense,
gas generation for use in the field provides a significant cost
benefit over conventional methods for generating a hydrogen rich
gas.
[0077] Process embodiments of the invention can take place as a
reforming reaction between 200 and 400.degree. C., dependent on the
fuel source and catalyst, and more preferably at about 400.degree.
C. As such, the reforming feed, i.e., fuel and water sources, are
heated to boiling temperature, vaporized, then continued to be
heated to the above temperature range, where they react to from
driver gas. After the reforming reaction, the gas product can be
cooled. The heat is provided by combustion of a fuel or via a
non-combustible source.
[0078] With regard to a combustible reaction to supply the energy
to drive the reforming reaction, a spark plug, incandescent wire,
or any other common ignition device is typically used to initially
start the reaction.
[0079] The following description is provided as an illustrative
example and is not meant to limit the description herein.
[0080] Step 1: Preheat Reformer Feed, Cooling of Gas
[0081] The reformer feed (fuel and water) enters the system at
20.degree. C. Use of methanol will be provided for illustrative
purposes. The average boiling temperature for the CH.sub.3OH and
H.sub.2O is .about.90.degree. C. Assuming as an example a small
system with a driver gas production rate of 100 standard liters per
minute, the heat required to preheat the reformer feed from 20 to
90.degree. C. is 202 J/s. The heat lost during this step is 4 J/s.
The aim of this heat exchanger is to have the gas exit at about
35.degree. C. Knowing the preheat will require a total of 206 J/s,
the inlet temperature of the hydrogen rich gas needed is calculated
to be 130.degree. C. A heat exchanger model shows that a total
length of 2.6 m of tube-in-tube exchanger is needed. Coiled, the
resulting height is about 9 cm.
[0082] Step 2: Begin Boiling Reformer Feed, Begin Cooling Gas
[0083] The hydrogen rich gas will be leaving the reaction chamber
at about 400.degree. C. As it cools to 130.degree. C., a heat of
613 J/s is produced, 16.5 J/s of which is lost. To vaporize the
CH.sub.3OH and H.sub.2O, 1308 J/s is needed. Therefore, the gas
partially boils the reformer feed. The total length of the
tube-in-tube required for this process is 2.1 m. When coiled, the
resulting height is about 7 cm. The heat exchangers for steps 1 and
2 are combined into a single unit.
[0084] Step 3: Finish Boiling Reformer Feed, Cool the Combustion
Gas
[0085] After Step 2, the reforming feed still needs 710 J/s to
finish vaporizing, and in this step, 42 J/s is lost. As calculated
in Step 5, the combustion gas will leave the reformer at about
648.degree. C. Giving the reforming feed the heat it needs to boil
brings the combustion gas temperature down to 127.degree. C. This
takes a length of 2.8 m of the tube-in-tube exchanger, which is
about 10 cm high when coiled.
[0086] Step 4: Finish Heating Reformer Feed
[0087] The reforming feed is already vaporized and will finish
heating when it contacts the top plate of a combustion chamber.
Heating the reforming feed from 90.degree. to 400.degree. C.
requires 518 J/s. This amount of heat brings the temperature of the
combustion gas from 1650.degree. to 1360.degree. C.
[0088] Step 5: Reforming Reaction
[0089] To reform CH.sub.3OH & H.sub.2O, 1080 J/s of power may
be used in this example. This section of the heat exchanger also
loses 94 J/s to the surroundings. Accommodating this, the
combustion gas temperature drops from 1360 to 648.degree. C. The
design length of this multiple tube section is about 20 cm.
[0090] An equation for determining the heat used or needed for
these processes is Q=.SIGMA.mC.sub.P.DELTA.T. The calculations led
to obtaining the .DELTA.H and heat lost across a given section and
the section's length. The heat exchange formulas and calculation
methods used for the reformer system design are given in Incropera
and DeWitt, 1996.
[0091] The following example is provided by way of illustration and
is not intended as limiting. An oil recovery estimate of a typical
embodiment of the present invention is provided herein. Based on
calculations described in U.S. Pat. No. 4,141,417 (incorporated by
reference herein) hydrogen was estimated to displace oil from
underground reservoirs with a usage of between 400 to 1200 SCF per
barrel, depending on the depth of the oil and other like factors.
As such, a value of 800 SCF of reformer gas is used in the
following calculation for each barrel of oil recovered.
[0092] One barrel of oil is equal to 42 gallons which weighs
approximately 126 kg. The 800 SCF is equal to 21,600 standard
liters, which is 982 moles of reformer gas. If the reformer is
using a crude petroleum as the reformer fuel, with an average
formula of CH.sub.2, then the reforming reaction can be represented
by reaction 13:
CH.sub.2+2H.sub.2O.fwdarw.CO.sub.2+3H.sub.2 Reaction 13
[0093] It can also be seen that the produced reformer gas has the
same mixture ratio as if it were commercial methanol as the
reformer fuel (see Reaction 2). The average molecular weight of the
reformer gas in both cases is 12.5 g/mole.
[0094] Accordingly, the 982 moles of reformer gas are equal to
12.275 kg, which produces 126 kg of oil or 0.097 kg reformer gas/kg
of oil.
[0095] However, in the case of Reaction 13, only 14/50 (0.28) of
the reformer gas owes its mass to the petroleum. In the case of
Reaction 2, 32/50 (0.64) of the reformer gas owes its mass to the
methanol.
[0096] Therefore, to produce one kg of oil, the reformer needs to
use either 0.097.times.0.28=0.027 kg of oil or
0.097.times.0.64=0.062 kg of methanol. Using the numbers from
Reaction 13, only 2.7% of the oil drawn from the well is required
in the reformer in order to drive the rest of the oil out of the
well. Alternatively, using the numbers from Reaction 2, 62 grams of
methanol is required for every kg of oil produced. Methanol
currently is selling for about $0.30/kg. With oil costing
approximately $63/barrel, oil is worth about $0.50/kg. In this
case, an amount of methanol worth 1.86 cents would recover
approximately 50 cents worth of oil, which is a methanol sacrifice
equal to 3.72% of the value of the oil produced.
[0097] This example shows that using either Reaction 13 or Reaction
2 is economically feasible for the recovery of oil from a depleted
oil well. The use of local petroleum appears to be more efficient,
but the use of commercial methanol as a reformer feed eliminates
the need to eliminate sulfur of other catalyst poisoning
contaminants from crude oil prior to catalyst reformation.
[0098] Importantly, the above example shows that the reformer
embodiments of the present invention, used for producing driver
gas, are much more efficient than the partial oxidation techniques
taught or suggested in U.S. Pat. No. 4,141,417 ('417). In
particular, the '417 patent shows only a partial oxidation reaction
that forms half as many moles of driver gas as produced by
embodiments of the present invention. Thus, the present invention
has double the efficiency of that shown in the prior art '417
patent.
[0099] While the methods disclosed herein have been described and
shown with reference to particular operations performed in a
particular order, it will be understood that these operations may
be combined, sub-divided, or re-ordered to form equivalent methods
without departing from the teachings of the present invention.
Accordingly, unless specifically indicated herein, the order and
grouping of the operations is not a limitation of the present
invention.
[0100] While the invention has been particularly shown and
described with reference to embodiments thereof, it will be
understood by those skilled in the art that various other changes
in the form and details may be made without departing from the
spirit and scope of the invention.
* * * * *